Extensive research and development has been undertaken in the UK on MarBN steels. These were first proposed by Professor Fujio Abe from NIMS in Japan. Within the UK, progress has been made towards commercialisation of MarBN-type steel through a series of Government funded industrial collaborative projects (IMPACT, IMPEL, INMAP and IMPULSE). As part of the IMPACT project, which was led by Uniper Technologies, boiler tubes were manufactured from the MarBN steel developed within the project, IBN1, and installed on the reheater drums of Units 2 and 3 of Ratcliffe-on-Soar Power Station. The trial tubes were constructed with small sections of Grade 91 tubing on either side of the IBN1 to allow direct comparison after the service exposure. This is the world’s first use of a MarBN steel on a full-scale operational power plant. In September 2018 the first tube was removed having accumulated 11,727 hours operation and 397 starts. This paper reports microstructural and oxidation analysis, that has been undertaken by Loughborough University as part of IMPULSE project, and outlines future work to be carried out.

In downstream oil industry applications, high-temperature sulfidation corrosion is generally caused by sulfur species coming from the crude; additionally, naphthenic acids or hydrogen can considerably worsen the corrosivity of the environment. During plant operations, several events may occur that boost the severity of corrosion: high feedstock turnover, with increasing “active” sulfur species; skin temperature rise due to the increasing insulation effect of the scale, generating an over-tempering of the material and possible degeneration into creep conditions. Thor115 is a ferritic steel with 11% chromium content to resist sulfidation. It has excellent creep properties for high temperature environments: higher allowable stresses than grade 91, keeping the same manufacturing and welding procedures. At the same time, it has the characteristics of ferritic steel, ensuring enhanced thermal conductivity and lower thermal expansion compared to austenitic steels. Comparative corrosion tests between Thor115 and other ferritic steels typically used in this industry (e.g., grade T/P5 and grade T/P9) have been carried out to simulate different corrosive conditions, confirming the superior properties of Thor115 relative to other ferritic grades. For these reasons, Thor 115 is a suitable replacement material for piping components that need an upgrade from grade T/P9 or lower, in order to reduce corrosion rate or frequency of maintenance operations.

A creep resistant martensitic steel, CPJ7, was developed with an operating temperature approaching 650°C. The design originated from computational modeling for phase stability and precipitate strengthening using fifteen constituent elements. Approximately twenty heats of CPJ7, each weighing ~7 kg, were vacuum induction melted. A computationally optimized heat treatment schedule was developed to homogenize the ingots prior to hot forging and rolling. Overall, wrought and cast versions of CPJ7 present superior creep properties when compared to wrought and cast versions of COST alloys for turbines and wrought and cast versions of P91/92 for boiler applications. For instance, the Larson Miller Parameter curve for CPJ7 at 650°C almost coincides with that of COST E at 620°C. The prolonged creep life was attributed to slowing down the process of the destabilization of the MX and M 23 C 6 precipitates at 650°C. The cast version of CPJ7 also revealed superior mechanical performance, well above commercially available cast 9% Cr martensitic steel or derivatives. The casting process employed slow cooling to simulate the conditions of a thick wall full-size steam turbine casing but utilized a separate homogenization step prior to final normalization and tempering. To advance the development of CPJ7 for commercial applications, a process was used to scale up the production of the alloy using vacuum induction melting (VIM) and electroslag remelting (ESR), and underlined the importance of melt processing control of minor and trace elements in these advanced alloys.

Development of steels used in the power generation industry for the production of boilers characterized by supercritical parameters poses new challenges. The introduction of new combinations of alloying agents aimed at obtaining the best possible mechanical properties, including creep resistance, affects the weldability of new steels. Each of the latter has to undergo many tests, particularly as regards bending and welding, in order to enable the development of technologies ensuring failure-free production and assembly of boiler systems. Martensitic steels containing 9% Cr, used in the manufacturing of steam superheaters, are characterized by excellent creep resistance and, at the same time, low oxidation resistance at a temperature in excess of 600°C. In turn, steels with a 12% Cr content, i.e., VM12-SHC or X20CrMoV12-1 are characterized by significantly higher oxidation resistance but accompanied by lower strength at higher temperatures, which translates to their limited application in the production of boilers operating at the most top parameters.X20CrMoV12-1 was withdrawn from most of the power plants, and VM12-SHC was supposed to replace it, but unfortunately, it failed in regards to creep properties. To fulfill the gap a new creep strength-enhanced ferritic steel for service in supercritical and ultra-supercritical boiler applications was developed by Tenaris and it is designated as Thor115 (Tenaris High Oxidation Resistance). This paper covers the experience gained during the first steps of fabrication, which includes cold bending and welding of homogenous joints.

A newly developed ferritic heat-resistant steel; 9Cr-3W-3Co-Nd-B steel has higher creep rupture strength both in the base metal and welded joints than the conventional high-Cr ferritic heat-resistant steels. The creep rupture strengths of 9Cr-3W-3Co-Nd-B steel welded joints were below the lower limit of the base metal in long-term creep stage more than 20,000 hours. The creep rupture position was heat-affected zone (HAZ) from 1.0 to 1.5 mm apart from the fusion line on the welded joint specimen ruptured at 34,966 hours. The equiaxed subgrains and coarsened precipitates were observed in HAZ of the ruptured specimen. In order to clarify the creep fracture mechanism of the welded joints, the microstructures of HAZ were simulated by heat cycle of weld, then observed by EBSD analysis. Fine austenite grains formed along the prior austenite grain boundaries in the material heated just above A C3 transformation temperature, however there were no fine grains such as conventional steel welded joints. The prior austenite grain boundaries were unclear in the material heated at 1050 °C. The creep rupture life of the material heated at just above A C3 transformation temperature exceeded the lower limit of base metal and there was no remarkable degradation, although it was shorter than the other simulated materials. It is, therefore, concluded that the creep fracture of 9Cr-3W-3Co-Nd-B steel welded joint in long-term stage occurred at HAZ heated at from just above A C3 transformation temperature to 1050 °C. It is speculated that the fine austenite grains formed along the prior austenite grain boundaries and inhomogeneous microstructures cause the coarsening precipitates and recovery of lath structure during long-term creep deformation.

Long-term creep rupture tests up to 10 5 hours at 600℃ and 650℃ were carried out on mod.9Cr- 1Mo steel base metal and weldments from five different materials, consisting of various chemical compositions and heat treatments as well as welding conditions. As a result, positive correlations of creep rupture strength were clarified between the base metal and weldments from the same materials. Microstructural observations and thermokinetic calculations revealed that the strength correlations were attributed to the precipitation strengthening behavior of finely dispersed M 23 C 6 carbides and V-type MX carbonitrides, where their precipitation distribution characteristic in the fine-grained HAZ microstructures partially or almost entirely took over those in base metal. This finding implies that the long-term creep rupture strength of mod.9Cr-1Mo steel weldment might be able to be evaluated as long as the corresponding base metal strength is obtained.

The formation of periodically arrayed rows of very fine Fe 2 Hf Laves phase particles was recently found in 9 wt. % chromium ferritic matrix through interphase precipitation along a reaction path of δ-ferrite → γ-austenite + Fe 2 Hf with a subsequent phase transformation of the γ phase into the α-ferrite phase. One of the problems on the formation of the fine Laves phase dispersion is a poor heat treatability; the interphase precipitation (δ-Fe→γ-Fe+Fe 2 Hf) is competitive with the precipitation of Laves phase from the δ phase in the eutectoid-type reaction pathway (δ→δ+Fe 2 Hf). In the present work, the effect of supersaturation on the precipitation of Laves phase from δ phase (δ→δ+Fe 2 Hf) and the δ→γ transformation in the reaction pathway was investigated by changing the Hf and Cr contents. The results obtained suggest that it is effective to have a high supersaturation for the precipitation of Laves phase and an adequately high supersaturation for the δ→γ transformation at the same time in order to widen the window of the interphase precipitation

To save fossil fuel resources and to reduce CO 2 emissions, considerable effort has been directed toward researching and developing heat-resistant materials that can help in improving the energy efficiency of thermal power plants by increasing their operational temperature and pressure conditions. Instead of conventional 9-12Cr ferritic heat-resistant steels with a tempered martensitic microstructure, we developed “Precipitation Strengthened 15Cr Ferritic Steel” based on a new material design concept: a solid-solution treated ferrite matrix strengthened by precipitates. Creep tests for 15Cr-1Mo-6W-3Co-V-Nb steels with ferrite matrix strengthened by a mainly Laves phase (Fe 2 W) showed that the creep strengths of 15Cr ferritic steel at temperatures ranging from 923 K to 1023 K were twice as high as those of conventional 9Cr ferric heat-resistant steel. 15Cr steels have higher steam oxidation resistance than that of conventional steel in the same temperature range as the creep tests. Thus, the new material design concept of heat-resistant steel pro- vides improved creep strength and steam oxidation resistance. We are attempting to determine the optimum compositions, especially that of carbon, in order to improve the high-temperature creep strength.

The microstructures of an advanced Ta-added 9Cr-3Co-2W-Mo steel with increased boron content that has been homogenized at different temperatures were investigated. The chains of coarse W-rich particles were observed in the steel after homogenization at 1150°C for 24 h. These particles remained in the microstructure after normalization and tempering. Such additional dispersion hardening in the initial state of the studied steel decreased the creep rate in transient region. However, the duration of steady state creep and overall creep time was increased in the samples homogenized at 1200°C. Despite of the presence of coarse W-rich particles, the impact toughness of the low-temperature- homogenized steel in the tempered condition was significantly higher than that of the steel homogenized at 1200°C

Creep strength enhanced ferritic steels like T/P 91 and T/P 92 are widely used for the fabrication of pressure vessel components in the petro-chemical and thermal power industry. Today, a new generation of 9-12% Cr CSEF steels like MARBN, Save12AD, G115 and Super VM12 are entering into the market. All CSEF steels require an accurate post-weld heat treatment after welding. This paper discusses the impact of chemical composition on Ac1 as well as the transformation behavior during post-weld heat treatment in a temperature range below and above Ac1. The Ac1 temperature of weld metals with variations in chemical composition has been determined and thermodynamic calculations has been carried out. Simulations of heat treatment cycles with variations in temperature have been carried out in a quenching dilatometer. The dilatation curves have been analyzed in order to detect any phase transformation during heating or holding at post weld heat treatment. Creep rupture tests have been carried out on P91 and Super VM12 type weld metals in order to investigate the effect of sub- and intercritical post weld heat treatment on creep rupture strength.

Modified 9Cr-1Mo alloy steel has been developed over the last few decades and has since gained wide acceptance in the boiler industry for the production of a variety of pressure-critical components, including tubing, piping and headers. The properties of creep-strength enhanced ferritic steels such as grade 91 are critically dependent on manufacturing parameters such as steelmaking, hot deformation, heat treatment and welding. Since the applications for which this material is used impose strict requirements in terms of resistance, corrosion, and creep behavior, poor process control can severely compromise the service behavior. This work discusses the impact of total deformation during the rolling process, and heat treatment parameters on time-independent and time-dependent properties for grade 91. For this study, two heats with similar chemical composition were produced with different reduction ratios: to which, several normalizing and tempering combinations were applied. For each combination, the microstructure was characterized, including evaluation of segregation by metallographic examination, and analysis of secondary phase precipitates by means of X-ray powder diffraction. Mechanical testing and creep testing were performed. A comparison of results is presented, and recommendations on the optimal process parameters are provided to ensure reliable performance of grade 91 material.

Microstructure change during creep at 650°C has been examined for a high-B 9%Cr steel by FIB-SEM serial sectioning 3D observation, Nano-SIMS, SEM, EBSD and TEM. The precipitates formed in the steel were M 23 C 6 , Laves phase, and a quite small amount of MX. For as-tempered steel, precipitation of M 23 C 6 on the prior austenite grain boundaries was clearly found, while precipitation of the Laves phase was not confirmed during tempering. The volume fraction of the Laves phase gradually increased with elapsed time, while M 23 C 6 appeared to increase once and decrease afterward, based on the comparison between the 2,754 h ruptured sample and the 15,426 h ruptured sample. Nano-SIMS measurements have revealed that B segregates on the prior austenite grain boundaries during normalizing, and it dissolves into M 23 C 6 .

Two materials with different purity of 2.25Cr-1Mo steel thick weld joint were prepared and creep rupture behavior was investigated by large sized specimens. For high purity material, two types of challenging heat treatment was tried to modify the original microstructural conditions. Weld joints were made and large sized creep test specimens were machined. Creep tests were performed at 903K, 40MPa. Specimen made from low purity material fractured at fine grained heat affected zone (FGHAZ) and showed so-called Type IV cracking. On the other hand, specimen made from high purity material showed maximum creep damage at weld metal. In the case of specimens applied challenging heat treatment, remarkably high ductility were observed at fracture. Regarding 2.25Cr-1Mo steel, it was confirmed that the suppression of Type IV cracking had been basically achieved by past improvement on purity level. At the same time, improvement of heat treatment condition was found to have further effect. Because of improved creep properties of high purity material, properties of weld metal had rose up to be the next issue to be examined. At least, taking care on layout design of weld beads to avoid creating wide spread fine grained portion is desired.

The creep strength and ductility of Grade P22 steel (2¼ Cr) was measured at 600°C under standard uniaxial tensile conditions at 150MPa. Test specimens were prepared by solution heat treatment at austenitization temperatures ranging from 900°C - 1200°C followed by normalization at 900°C before continuous air cooling to room temperature. In addition to specimens tested in the solution treated state, creep tests were also performed after tempering. The variable austenitization temperatures gave rise to different prior austenite grain (PAG) sizes, which in turn influenced the crystallographic packet and block boundary misorientation angle distribution. The latter parameters were measured using electron backscattered diffraction which also allowed partial reconstruction of the PAG boundaries. The time to creep failure at 600°C increased as function of PAG size up to approximately 70µm, but significantly decreased when the average prior austenite grain size measured approximately 108 µm. However, the minimum creep rate decreased even up to the largest PAG size with corresponding decrease in creep ductility. The stability of the crystallographic packet and block boundaries influences the high strength-low ductility for the large PAGs in comparison to the dominant effect of PAG boundaries at the smallest grain size where extensive recovery and recrystallization reduces creep strength.

Creep strength degradation behavior of normalized and tempered 2.25Cr-1.6W-V-Nb(Gr.23) steel was investigated by conducting extra long-term creep rupture tests. Creep strength drop was observed in long-term creep range at 600°C and above, while signs of a creep strength drop were not identified at 550°C and 575°C. Creep strength drop of around 110 MPa at 600°C was caused not by the effect of oxidation but rather by a change of the deformation mechanism or the weakening of deformation resistance by the microstructural change during creep. The effect of oxidation was significant for causing a further creep strength drop in the range which exceeded 20,000 h in rupture time at 600°C. As a result, the creep strength at 60 MPa and 600°C was almost the same regardless of long tempered or aged steel.

A new ferritic steel branded as Thor 115 has been developed to enhance high-temperature resistance. The steel design combines an improved oxidation resistance with long-term microstructural stability. The new alloy was extensively tested to assess the high-temperature time- dependent mechanical behavior (creep). The main strengthening mechanism is precipitation hardening by finely dispersed carbide (M 23 C 6 ) and nitride phases (MX). Information on the evolution of secondary phases and time-temperature-precipitation behavior of the alloy, essential to ensure long-term stability, was obtained by scanning transmission electron microscopy with energy dispersive spectroscopy, and by X-ray powder diffraction on specimens aged up to 50,000 hours. The material behavior was also tested in service conditions, to validate the laboratory results: Thor 115 tubing was installed in a HRSG power plant, directly exposed to turbine flue gasses. Tubing samples were progressively extracted, analyzed and compared with laboratory specimens in similar condition. This research shows the performance of Thor 115 regarding steam oxidation and microstructure evolution up to 25,000 exposure hours in the field. So far, no oxide microstructure difference is found between the laboratory and on field tubing: in both cases, the oxide structure is magnetite/hematite and Cr-spinel layers and the oxide thickness values lay within the same scatter band. The evolution of precipitates in the new alloy confirms the retention of the strengthening by secondary phases, even after long-term exposure at high temperature. The deleterious conversion of nitrides into Z phase is shown to be in line with, or even slower than that of the comparable ASME grade 91 steel.

The newly developed 12%Cr steel Super VM12 is characterized by excellent creep rupture strength properties (better than Grade 92) and enhanced steam oxidation resistance of 12%Cr steels such as VM12-SHC. Balanced properties profile of the new steel development in comparison to the existing well-established steels such as Grade 91 and Grade 92, opens opportunities for its application as construction material for components in existing or future high-efficiency power plants. In this study the oxidation behavior of typical 9%Cr steels was compared with the new steel development. The oxide scale morphologies and compositions of different oxide layers as function of temperature and exposure time in steam-containing atmospheres were characterized using light optical metallography, Scanning Electron Microscopy (SEM). Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected creep specimens were investigated using the Transmission Electron Microscopy and the Atom Probe Tomography techniques.

9-10%Cr-3%Co martensitic steels are the prospective materials for elements of boilers, tubes and pipes for fossil power plants which are able to work at ultra-supercritical parameters of steam (T=620-650°C, P=25-30 MPa). The effect of creep on the microstructure of the 10 wt.%Cr-3Co- 3W-0.2Re martensitic steel was investigated in the condition of 650°C and an applied stress of 140 MPa, time to rupture was more than 8500 h. Previously, this steel was subjected to the normalizing at 1050°C and tempering at 770°C. This heat treatment provided the hierarchical tempered martensite lath structure with the mean size of prior austenite grains of 59 μm and with high dislocation density (2×10 14 m -2 ) within martensitic laths. Boundary M 23 C 6 and M 6 C carbides and randomly distributed within matrix Nb-rich MX carbonitrides were detected after final heat treatment. The addition of Re in the steel studied positively affected creep at 650°C/140 MPa and stabilized the tempered martensite lath structure formed during 770°C-tempering. The formation of the subgrains in the gage section was accompanied by the coarsening of M 23 C 6 carbides and precipitations of Laves phase with fine sizes during creep. No depletion of Re and Co from the solid solution during creep was revealed whereas W content decreased from 3 to 1 wt.% for first 500 h of creep. Reasons of improved creep as well as mechanisms of grain boundary pinning by precipitates are discussed.

The size and distribution of the Laves phase particles in a 9.85Cr-3Co-3W-0.13Mo-0.17Re- 0.03Ni-0.23V-0.07Nb-0.1C-0.002N-0.008B steel subjected to creep rupture test at 650°C under an applied stresses of 160-200 MPa with a step of 20 MPa were studied. After heat treatment consisting of normalizing of 1050°C and tempering of 770°C, M 23 C 6 and Fe 3 W 3 C carbides with the mean sizes of 67±7 and 40±5 nm, respectively, were revealed along the boundaries of prior austenite grains and martensitic laths whereas round NbX carbonitrides were found within martensitic laths. During creep metastable Fe 3 W 3 C carbides dissolved and the stable Laves phase particles precipitated; volume fraction of Laves phase increases with time. The Laves phase particles nucleated on the interfacial boundaries Fe 3 W 3 C/ferrite during first 100 h of creep and provided effective stabilization of tempered martensitic lath structure until their mean size less than 150 nm.

Modified 9Cr-1Mo steel (ASTM Gr.91) is widely used in components of fossil fueled power plants around the world today. This grade of steel has however been shown to exhibit significant variations in creep life and creep ductility, which has led to premature in-service failures. The aim of this work is to define potential metallurgical risk factors that lead to this variation in performance. To achieve this, a set of creep test samples that represent a wide range in this variation of creep behavior in this steel grade have been studied in detail. As a first stage in this characterization the macro-scale chemical homogeneity of the materials were mapped using micro-XRF. Understanding the segregation behavior also allows quantification of microstructural parameters in both segregated and non-segregated areas enabling the variations to be determined. For example this showed a significant increase in the number per unit area of Laves phase particles in high compared with low Mo content areas. To study the effect of MX particles on segregation a methodology combining SEM and TEM was employed. This involved chemically mapping the larger V containing particles using EDS in the SEM in segregated and unsegregated areas and then comparing the results to site-specific TEM analysis. This analysis showed that although the average size of the V containing samples is in the expected 0-50 nm size range, these particles in some samples had a wide size distribution range, which significantly overlaps with the M 23 C 6 size distribution range. This together with the segregation characteristics has important implications for determining meaningful quantitative microstructural data from these microstructurally complex materials.